Effect of sputtering pressure and post-annealing on hydrophilicity of TiO2 thin films deposited by reactive magnetron sputtering

A series of TiO₂ thin films was deposited onto glass substrates without intentional heating or biasing by magnetron sputtering of a titanium target using Ar/O₂ reactive mixtures over a broad range of total sputtering pressures from 0.12 Pa to 2.24 Pa. Each of the film types was deposited by the threshold poisoned mode at a specific given oxygen flow rate monitored in-situ by optical emission spectroscopy. Both the sputtering pressure and thermal annealing are the key factors for the TiO₂ films to yield fast-response superhydrophilicity with a water contact angle of 5°. The mechanism of superhydrophilicity for the TiO₂ films deposited by high-pressure sputtering will be discussed based on empirical studies of X-ray diffractometry, high-resolution scanning microscopy and atomic force spectroscopy.     

Structural and electrical properties of thin Ho2O3 gate dielectrics

This paper describes the structural properties and electrical characteristics of thin Ho₂O₃ gate dielectrics deposited on silicon substrates by means of reactive sputtering. The structural and morphological features of these films after postdeposition annealing were studied by X-ray diffraction, atomic force microscopy, and X-ray photoelectron spectroscopy. It is found that Ho₂O₃ dielectrics annealed at 700 °C exhibit a thinner capacitance equivalent thickness and excellent electrical properties, including the interface trap density and the hysteresis in the capacitance-voltage curves. Under constant current stress, the Weibull slope of the charge-to-breakdown of the 700 °C-annealed films is about 1.7. These results are attributed to the formation of well-crystallized Ho₂O₃ structure and the reduction of the interfacial SiO₂ layer.     

Structure and microwave dielectric properties of Bi1.5Zn1.0Nb1.5O7 thin films deposited on alumina substrates by pulsed laser deposition

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films were deposited on polycrystalline alumina substrates by pulsed laser deposition at different substrate temperatures. The phase structure and surface morphology were characterized using X-ray diffractometer (XRD) and atomic force microscopy. Microwave dielectric properties were performed using split-post dielectric resonator method at spot frequencies of 10, 15 and 19 GHz, respectively. The XRD results indicate that the as-deposited Bi_1.5Zn_1.0Nb_1.5O₇ thin films deposited at 650 °C are amorphous in nature. The dielectric permittivity and loss tangent of the amorphous BZN thin films are 75.5 and 0.013 at 10 GHz, respectively. As the measure frequency increased to 19 GHz, the dielectric permittivity slightly decreases and loss tangent slightly increases. BZN thin films were crystallized after the post-annealing by a rapid thermal annealing in air for 30 min. The crystallized BZN thin films exhibit the excellent dielectric properties and frequency responses. The dielectric permittivity and loss tangent of the crystallized BZN thin films are 154 and 0.038 at 10 GHz, respectively.     

Low temperature preparation of transparent, antireflective TiO2 films deposited at different O2/Ar ratios by microwave electron cyclotron resonance magnetron sputtering

A serial of crystalline titanium oxide ceramic films were deposited at low temperature using microwave electron cyclotron resonance (MW-ECR) magnetron sputtering with different O₂/Ar ratios. The influences of O₂/Ar ratio on the deposition rate, morphology, crystalline nature, optical adsorption property of the obtained titanium oxide thin films were investigated by means of X-ray diffraction (XRD), atomic force microscopy (AFM) and UV-Vis spectra. Therefore, the optimum O₂/Ar ratio for deposition of anatase TiO₂ thin films on unheated glass substrate was realized in a MW-ECR magnetron sputtering process. The as-deposited anatase TiO₂ films were transparent and were antireflective in the visible region.     

Structural and optical studies of nanocrystalline V2O5 thin films

We report the structural and optical properties of nanocrystalline thin films of vanadium oxide prepared via evaporation technique on amorphous glass substrates. The crystallinity of the films was studied using X-ray diffraction and surface morphology of the films was studied using scanning electron microscopy and atomic force microscopy. Deposition temperature was found to have a great impact on the optical and structural properties of these films. The films deposited at room temperature show homogeneous, uniform and smooth texture but were amorphous in nature. These films remain amorphous even after postannealing at 300 °C. On the other hand the films deposited at substrate temperature T_S > 200 °C were well textured and c-axis oriented with good crystalline properties. Moreover colour of the films changes from pale yellow to light brown to black corresponding to deposition at room temperature, 300 °C and 500 °C respectively. The investigation revealed that nanocrystalline V₂O₅ films with preferred 001 orientation and with crystalline size of 17.67 nm can be grown with a layered structure onto amorphous glass substrates at temperature as low as 300 °C. The photograph of V₂O₅ films deposited at room temperature taken by scanning electron microscopy shows regular dot like features of nm size.     

Structural, optical and electrical properties of reactively sputtered Ag2Cu2O3 films

Ag₂Cu₂O₃ thin films were deposited on glass substrates by RF magnetron sputtering of an equiatomic silver-copper target (Ag_0.5Cu_0.5) in reactive Ar-O₂ mixtures. The reactive sputtering was done at varying power, oxygen flow rate and deposition temperature to study the influence of these parameters on the deposition of Ag₂Cu₂O₃ films. The film structure was determined by X-ray diffraction, while the optical properties were examined by spectrophotometry (UV-vis-NIR) and photoluminescence. Furthermore, the film thickness and resistivity were measured by tactile profilometry and 4-point probe, respectively. Additional mobility, resistivity and charge carrier density Hall effect measurements were done on a few selected samples. The best films in terms of stoichiometry and crystallography were achieved with a sputtering power of 100 W, oxygen and argon flow rates of 20 sccm (giving a deposition pressure of 1.21 Pa) and a deposition temperature of 250 °C. The optical transmittance and photoluminescence spectra of films deposited with these parameters indicate several band gaps, most prominently, a direct one of around 2.2 eV. Electrical characterization reveals charge carrier concentrations and mobilities in the range of 10²¹-10²² cm^− 3 and 0.01-0.1 cm²/Vs, respectively.     

Chemistry of post-annealing of epitaxial CoFe2O4 thin films

CoFe₂O₄ thin films of different thicknesses were grown on SrTiO₃ substrates. The X-ray diffraction analysis and atomic force microscopy indicated both epitaxy and a granular microstructure. We studied the magnetic properties of these films as a function of oxygen post-annealing and film thickness. All as-deposited films exhibited similar magnetic properties with saturated magnetization (M_s) of approximately 50% of the bulk M_s, (80 Am² kg^− 1). After the post-annealing the M_s changes as a consequence of crystallographic restructuring of the film. Cation ordering in 100 nm thick films reduces M_s, whereas re-oxidation increases M_s for thinner films. 13 nm films, annealed for 1 h, reach the bulk M_s. For even thinner films the quantum-size effect reduces M_s. For a synthesis of ≥ 30 nm films an annealing cycle after deposition of every 15 nm layer is recommended.     

Fabrication and characterization of Fe3O4 thin films deposited by reactive magnetron sputtering

Fe-O thin films with different atomic ratio of iron to oxygen were deposited on glass and thermally oxidized silicon substrates at temperatures of 300, 473 and 593 K, by reactive magnetron sputtering in Ar+O₂ atmosphere. The composition and structure of the thin films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrical resistivity. It was found from XRD that with increasing the oxygen partial pressure in the working gas, the crystalline structure of the Fe-O films deposited at the substrate temperature of 473 K gradually changed from α-Fe, amorphous Fe-O, Fe₃O₄, γ-Fe₂O₃ to Fe_21.34O₃₂. The structure and chemical valence of the Fe₃O₄ films were analyzed by electron microscopy and XPS, respectively.     

Dip coated 12CaO·7Al2O3 thin films through sol-gel process using metal alkoxide

Transparent nanostructured 12CaO·7Al₂O₃ thin films with cubic structure have been prepared on soda lime glass substrates via the sol-gel dip coating using the precursor sol solution at low temperature. The structural, compositional, morphological and optical properties of the 12CaO·7Al₂O₃ films and powder were studied using X-ray diffractometry (XRD), X-ray photoelectron spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy. Optical properties of 12CaO·7Al₂O₃ films have been investigated using UV-visible spectroscopy. Two different precursor sols were prepared using calcium-2-ethyl hexonate and aluminium isopropoxide as precursor materials in isopropanol and ethylene glycol monomethyl ether solvents. Dip coated gel like films were dried at 120 °C for 15 min and subsequently heat-treated at 450 °C for 1 h in air atmosphere. The influence of films thickness and optical transparency with use of different solvent and sol concentration on microstructure of the films were established. In addition, XRD patterns revealed that 12CaO·7Al₂O₃ films have been composed of cubic phase. SEM observations exhibited that the films structure becomes more homogeneous using isopropanol as compared to ethylene glycol monomethyl ether solvent. The 12CaO·7Al₂O₃ films prepared using 2 (wt.%) sol in isopropanol had high transparency nearly 88% in wide visible range with maximum of 90% at 600 nm wavelength.     

Effect of high temperature post-annealing of La0.7Sr0.3MnO3 films deposited by radio frequency magnetron sputtering on SiO2/Si substrates heated at low temperature

La_0.7Sr_0.3MnO₃ thin films were deposited on SiO₂/Si substrates by RF magnetron sputtering under different oxygen gas flow rates with a sputtering power of 100 W. During deposition, the substrate was heated at 623 K. To investigate post-annealing effects, the as-deposited La_0.7Sr_0.3MnO₃ thin films were thermal-treated at 973 K for 1 h. The effects of oxygen gas flow rate and post-annealing treatment on the physical properties of the films were systematically studied. X-ray diffraction results show that the growth orientation and crystallinity of the films were greatly affected by the oxygen gas flow rate and substrate heating during deposition. The sheet resistance of the films gradually decreased with increasing oxygen gas flow rate, while the post-annealed films showed the opposite behavior. The temperature coefficient of resistance at 300 K of La_0.7Sr_0.3MnO₃ thin films deposited at an oxygen gas flow rate of 40 sccm decreased from − 2.40%/K to − 1.73%/K after post annealing. The crystalline state of the La_0.7Sr_0.3MnO₃ thin films also affected its electrical properties.     

The effects of O2/Ar ratio on the structure and properties of hafnium dioxide (HfO2) films

HfO₂ films at various O₂/Ar flow ratios were prepared by reactive dc magnetron sputtering. The effects of O₂/Ar ratio on the structure and properties of HfO₂ films were studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and UV-Visible spectroscopy. The results showed that the HfO₂ films were amorphous at different O₂/Ar ratios, and the atomic ratio of O/Hf in the HfO₂ films at high O₂/Ar ratio was nearly to 2:1. The peaks of Hf4f and O1s shifted to higher binding energy with increasing the oxygen flow proportion. The HfO₂ films at high O₂/Ar ratio had high transmissivity at the range of 400-1100 nm.     

Laser annealing of Pb(Zr0.52Ti0.48)O3 thin films for the pyroelectric detectors

Lead zirconate titanate (Pb(Zr_0.52Ti_0.48)O₃, PZT) thin films fabricated by magnetron sputtering technique on the Pt/Ti/SiO₂/Si substrates at room temperature, were annealed by means of CO₂ laser with resulting average substrate temperature below 500 °C. The crystal structure, surface morphology and pyroelectric properties of the PZT films before and after annealing were investigated by X-ray diffraction, atomic force microscopy, and pyroelectric measurements. The results show that the annealed PZT thin film with a laser energy density of 490 W/cm² for 25 s has a typical perovskite phase, uniform crystalline particles with a size of about 90 nm, and a high pyroelectric coefficient with 1.15 × 10^− 8 Ccm^− 2 K^− 1.     

Annealing effect on structural and electrical properties of thermally evaporated Cd1−xMnxS nanocrystalline films

Thin films of Cd_1−xMn_xS (0 ≤ x ≤ 0.5) were deposited on glass substrates by thermal evaporation. All the films were deposited at 300 K and annealed at 573 K. The as-deposited and the annealed films were characterized for composition, structure and microstructure by using energy-dispersive analysis for X-rays, X-ray diffraction, scanning electron microscopy and atomic force microscopy. Electrical conductivity was studied in the temperature range 190-450 K. All the films exhibited wurtzite structure of the host material with the grain size varying in the range between 36 and 82 nm. Resistivity of all the films is strongly dependent on Mn content and annealing temperature and lies in the range 13-160 Ω cm.     

Comparison of hydrophilic properties of TiO2 thin films prepared by sol-gel method and reactive magnetron sputtering system

This article reports on preparation, characterization and comparison of TiO₂ films prepared by sol-gel method using the titanium isopropoxide sol (TiO₂ coating sol 3%) as solvent precursor and reactive magnetron sputtering from substoichiometric TiO_2 − x targets of 50 mm in diameter. Dual magnetron supplied by dc bipolar pulsed power source was used for reactive magnetron sputtering. Depositions were performed on unheated glass substrates. Comparison of photocatalytic properties was based on measurements of hydrophilicity, i.e. evaluation of water contact angle on the film surface after UV irradiation. It is shown, that TiO₂ films prepared by the sol-gel method exhibited higher hydrophilicity in the as-deposited state but has significant deterioration of hydrophilicity during aging, compared to TiO₂ films prepared by magnetron sputtering. To explain this effect AFM, SEM and high resolution XPS measurements were performed. It is shown that the deterioration of hydrophilicity of sol-gel TiO₂ films can be suppressed if as-deposited films are exposed to the plasma of microwave oxygen discharge.     

Study of the deposition parameters and Fe-dopant effect in the photocatalytic activity of TiO2 films prepared by dc reactive magnetron sputtering

The reactive magnetron sputtering method was used to prepare pure and Fe-doped titanium dioxide thin films. The films were deposited onto microscope glass slides and polycarbonate plates at different total pressure and Fe-doping concentrations. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-visible spectroscopy (UV). For glass substrates a polycrystalline TiO₂ structure was verified with X-ray diffraction, which showed typical characteristic anatase reflections. An iron phase appeared in the highly Fe-doped samples. The absorption edges of the Fe-doped TiO₂ films shifted to visible region with increasing concentration of iron. For the polycarbonate substrate an amorphous TiO₂ structure was revealed for all deposition conditions. The effects of different Fe-doping and total pressure levels on the photocatalytic activity were obtained by the degradation rates of Rhodamine-B (RoB) dye under UV light irradiation. For the deposition conditions considered in this study the highest photodegradation rates were achieved for films deposited on the polymer substrates. Of these overall highest rates was achieved for deposition at 0.4 Pa and without doping. However, for both substrates, films prepared at the particular total pressure of 0.5 Pa and a low iron concentration showed better photocatalytic activity than the pure TiO₂ films prepared under the same deposition parameters. On the contrary, the photocatalytic degradation rates of RoB on the highly Fe-doped TiO₂ films decreased strongly.     

Structural and temperature-related disordering studies of Cu6PS5I amorphous thin films

Cu₆PS₅I thin films were deposited onto silicate glass substrates by non-reactive radio frequency magnetron sputtering. Spectrometric and isoabsorption studies of Cu₆PS₅I thin films in the temperature interval 77-500 K were performed. Structural studies were carried out using X-ray diffraction and scanning electron microscopy techniques. Temperature evolution of optical transmission spectra as well as temperature dependences of optical pseudogap and Urbach energy is investigated. The influence of temperature-related and structural disordering on the Urbach tail is studied.     

Influences of post-annealing on structural and electrical properties of Bi1.5Zn1.0Nb1.5O7 thin films prepared by pulsed laser deposition

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films were prepared on Pt/TiO₂/SiO₂/Si(100) substrates at 650 °C under an oxygen pressure of 10 Pa by using pulsed laser deposition process. The crystallinity, microstructure and electrical properties of BZN thin films were investigated to verify the influences of post-annealing thermal process on them. The X-ray diffractometer (XRD) results indicate that all Bi_1.5Zn_1.0Nb_1.5O₇ thin films without post-annealing process or with post-annealing in situ vacuum chamber and in oxygen ambient exhibit a cubic pyrochlore structure. The improved crystallinity of BZN thin films through post-annealing was confirmed by XRD and scanning electron microscope (SEM) analysis. Dielectric constant and loss tangent of the as-deposited BZN thin films are 160 and 0.002 at 10 kHz, respectively. After annealing, dielectric properties of thin films are significantly improved. Dielectric constant and loss tangent of the in situ annealed films are 181 and 0.0005 at 10 kHz, respectively. But the films post-annealed in O₂ oven show the largest dielectric constant of 202 and the lowest loss tangent of 0.0002, which may attribute to the increase in grain size and the elimination of oxygen vacancies. Compared with the as-deposited BZN thin films, the post-annealed films also show the larger dielectric tunability and the lower leakage current density.     

Synthesis and characterization of beta barium borate thin films obtained from the BaO-B2O3-TiO2 ternary system

This work reports on the synthesis and the structural and optical characterization of beta barium borate (β-BBO) thin films containing 4, 8 and 16 mol% of titanium oxide (TiO₂) deposited on fused silica and silicon (0 0 1) substrates using the polymeric precursor method. The thin films were characterized by X-ray diffraction, Raman spectroscopy, atomic force microscopy and scanning electron microscopy techniques. The optical transmission spectra of the thin films were measured over a wavelength range of 800-200 nm. A decrease was observed in the band gap energy as the TiO₂ content was raised to 16 mol%. Only the β-BBO phase with a preferential orientation in the (0 0 l) direction was obtained in the sample containing 4 mol% of TiO₂ and crystallized at 650 °C for 2 h.     

High-rate deposition of high-quality Sn-doped In2O3 films by reactive magnetron sputtering using alloy targets

Sn-doped In₂O₃ (ITO) films were deposited on heated (200 °C) fused silica glass substrates by reactive DC sputtering with mid-frequency pulsing (50 kHz) and a plasma control unit combined with a feedback system of the optical emission intensity for the atomic O* line at 777 nm. A planar In-Sn alloy target was connected to the switching unit, which was operated in the unipolar pulse mode. The power density on the target was maintained at 4.4 W cm^− 2 during deposition. The feedback system precisely controlled the oxidation of the target surface in “the transition region.” The ITO film with lowest resistivity (3.1 × 10^− 4 Ω cm) was obtained with a deposition rate of 310 nm min^− 1 and transmittance in the visible region of approximately 80%. The deposition rate was about 6 times higher than that of ITO films deposited by conventional sputtering using an oxide target.     

Atomic layer deposition and post-deposition annealing of PbTiO3 thin films

Lead titanate thin films were deposited by atomic layer deposition on Si(100) using Ph₄Pb and Ti(O-i-Pr)₄ as metal precursors and O₃ and H₂O as oxygen sources. The influence of the Ti : Pb precursor pulsing ratio on the film growth, stoichiometry and quality was studied at two different temperatures, i.e. 250 and 300 °C. Uniform and stoichiometric films were obtained using a Ti : Pb precursor pulsing ratio of 1 : 10 at 250 °C or 1 : 28 at 300 °C. The as-deposited films were amorphous but the crystalline PbTiO₃ phase was obtained by rapid thermal annealing at 600-900 °C both in N₂ and O₂ ambient. Thin PbTiO₃ films were visually uniform and roughness values for as-deposited and annealed films were observed by atomic force microscopy.