Photocatalytic and antibacterial properties of TaON-Ag nanocomposite thin films

TaON-Ag nanocomposite thin films with Ag nano-particles embedded in TaON were prepared by reactive co-sputtering of Ta and Ag in the plasma of (O₂ + N₂)/Ar. The deposition temperature was either at room temperature or 300 °C. These films were characterized mainly by UV-Vis photometry and scanning electron microscopy. It is found that Ag doping into the TaON films leads to several beneficial changes on film properties. It would reduce the optical band gap and, therefore, enhance the films' photocatalytic behavior. It is also found that Ag nano-particles may emerge on the surface of TaON with or without RTA. This could be much meaningful since Ag particles' appearance is closely related to the antibacterial property of TaON-Ag films. The results show that TaON-Ag films deposited at 300 °C have an outstanding antibacterial behavior with the illumination of visible light due to the synergistic effects of Ag and photocatalytic behavior of TaON.     

Characterization of N-doped TiO2 films prepared by reactive sputtering using air/Ar mixtures

Nitrogen-doped titanium dioxide (TiO_2 − xN_x) thin films desirable for visible light photocatalysts were prepared by reactive sputtering using air/Ar mixtures. Using air as the reactive gas allows the process to conduct at high base pressures (low vacuum), which reduces substantially the processing time. The obtained films transformed from mixed phases to anatase phase as the air/Ar flow ratio increased. Substitutional doping of nitrogen verified by X-ray photoelectron spectroscopy accounts for the red-shift of absorption edge in the absorption spectra. Anatase TiO_2 − xN_x films could incorporate up to about 7.5 at.% substitutional nitrogen and a maximum of 23 at.% nitrogen was determined in the films with mixed phases. The optical band gaps of the TiO_2 − xN_x films calculated from Tauc plots varied from 3.05 to 3.11 eV and those of the mixed phase ranged from 2.77 to 3.00 eV, which are all lower than that for pure anatase TiO₂ and fall into the visible light regime.     

Photoelectrochemical and optical properties of N-doped TiO2 thin films prepared by oxidation of sputtered TiNx films

Nitrogen-doped titanium dioxide thin films with visible light photoresponse were prepared by oxidation of sputtered TiN_x films, whose nitrogen contents can be easily changed by controlling the volume ratio of N₂/(Ar + N₂) during reactive direct current (DC) magnetron sputtering process. The reference TiO₂ sample was also deposited by the same method under Ar/O₂ gas mixture. The as-prepared films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoemission spectroscopy, UV-vis spectrophotometry and photoelecrochemical measurements. The formation of anatase type TiO₂ is confirmed by XRD. SEM measurement indicates a rough surface morphology with sharp, protruding modules after annealing treatment. Optical properties reveal an extended tailing of the absorption edge toward the visible region due to nitrogen presence. The band gap of the N-doped sample is reduced from 3.36 eV to 3.12 eV compared with the undoped one. All the N-doped samples show red shift in photoresponse towards visible region and improved photocurrent density under visible irradiance is observed for the N-doped samples.     

Thin film preparation and characterization of wide band gap Cu3TaQ4 (Q = S or Se) p-type semiconductors

The structural, optical, and electronic properties of thin films of a family of wide band gap (E_g > 2.3 eV) p-type semiconductors Cu₃TaQ₄ (Q = S or Se) are presented. Thin films prepared by pulsed laser deposition of ceramic Cu₃TaQ₄ targets and ex-situ annealing of the as-deposited films in chalcogenide vapor exhibit mixed polycrystalline/[100]-directed growth on amorphous SiO₂ substrates and strong (100) preferential orientation on single-crystal yttria-stabilized zirconia substrates. Cu₃TaS₄ (E_g = 2.70 eV) thin films are transparent over the entire visible spectrum while Cu₃TaSe₄ (E_g = 2.35 eV) thin films show some absorption in the blue. Thin film solid solutions of Cu₃TaSe_4 − xS_x and Cu₃TaSe_4 − xTe_x can be prepared by annealing Cu₃TaSe₄ films in a mixed chalcogenide vapor. Powders and thin films of Cu₃TaS₄ exhibit visible photoluminescence when illuminated by UV light.     

Optoelectronic properties of sputter-deposited Cu2O-Ag-Cu2O treated with rapid thermal annealing

Cu₂O and two types of Cu₂O-Ag-Cu₂O (CAC) multilayered thin films were deposited on glass substrates using DC-magnetron sputtering. For CAC films, the mass thickness of Ag layer was controlled at 3 nm. After deposition, some of these films were annealed using a rapid thermal annealing (RTA) system at 650 °C, in order to create embedded Ag particles. AC films were used to study the clustering effect of Ag in Ar atmosphere, as well as for forming the 2nd type of CAC film by covering another Cu₂O layer on the annealed AC structure. A UV-VIS-NIR photometer, a Hall measurement system, and a I-V measurement system were used to characterize the optical and electrical properties of these films with and without RTA. The results show that 2-dimensional Ag layer can transform into many individual particles due to its high surface tension at annealing temperature, no matter when the annealing was carried out. For CAC films, without annealing, the optical transmission and the resistivity are decreased with the inserted Ag layer. After annealing, both the transmission and resistivity are increased, possibly due to the clustering effect of Ag layer. Most importantly, it is found that the embedded Ag particles can increase the light absorption in the NIR-IR region, which can increase photo-induced current.     

Stability and effect of annealing on the optical properties of plasma-deposited Ta2O5 and Nb2O5 films

Tantalum and niobium oxide optical thin films were prepared at room temperature by plasma-enhanced chemical vapor deposition using tantalum and niobium pentaethoxide (M(OC₂H₅)₅) precursors. We studied the evolution of their optical and microstructural properties as a result of annealing over a broad temperature range from room temperature up to 900 °C. The as-deposited films were amorphous; their refractive index, n, and extinction coefficient, k, at 550 nm were n = 2.13 and k < 10^− 4 for Ta₂O₅, and n = 2.24 and k < 10^− 4 for Nb₂O₅. The films contained a small amount of residual carbon (∼ 2-6 at.%) bonded mostly to oxygen. During annealing, the onset of crystallization was observed at approximately T_C1 = 650 °C for Ta₂O₅ and at T_C1 = 450 °C for Nb₂O₅. Upon annealing close to T₁ (300 °C for Nb₂O₅ and 400 °C for Ta₂O₅), n at 550 nm decreased by less than 1%. This was correlated with the decrease of carbon content, as suggested by Fourier transform infrared spectroscopy, elastic recoil detection and static secondary ion mass spectroscopy (SIMS) results. During annealing, we observed phase transition from the δ- (hexagonal) phase to the L- (orthorhombic) phase between 800 °C and 900 °C for Ta₂O₅, and between 600 °C and 700 °C for Nb₂O₅. The structural changes were also marked by silicon diffusion from the substrate into the oxide layer at annealing temperatures above 500 °C for Ta₂O₅ and above 400 °C for Nb₂O₅. As a consequence of oxygen, silicon and metal interdiffusion, the interface between the Si substrate and the metal oxide (Ta₂O₅ or Nb₂O₅) is characterized by its broadening, well documented by spectroscopic ellipsometry and SIMS data.     

The effect of nitrogen on the properties of zinc nitride thin films and their conversion into p-ZnO:N films

Zinc nitride thin films were deposited by magnetron sputtering using ZnN target in plasma containing either N₂ or Ar gases. The rf-power was 100 W and the pressure was 5 mTorr. The properties of the films were examined with thermal treatments up to 550 °C in N₂ and O₂ environments. Films deposited in Ar plasma were opaque and conductive (ρ ∼ 10^− 1 to 10^− 2 Ω cm, N_D ∼ 10¹⁸ to 10²⁰ cm^− 3) due to excess of Zn in the structure. After annealing at 400 °C, the films became more stoichiometric, Zn₃N₂, and transparent, but further annealing up to 550 °C deteriorated the electrical properties. Films deposited in N₂ plasma were transparent but very resistive even after annealing. Both types of films were converted into p-type ZnO upon oxidation at 400 °C. All thermally treated zinc nitride films exhibited a shoulder in transmittance at around 345 nm which was more profound for the Ar-deposited films and particularly for the oxidized films. Zinc nitride has been found to be a wide band gap material which makes it a potential candidate for transparent optoelectronic devices.     

Gravitational waves detector mirrors: Spectroscopic ellipsometry study of Ta2O5 films on SiO2 substrates

A stack of Ta₂O₅/SiO₂ layers is presently used as coating layer of mirrors in interferometric detectors for gravitational waves. The sensitivity of these detectors is limited in the 50-300 Hz frequency range by the mirror thermal noise, and it was suggested that mechanical losses in the Ta₂O₅ are the dominant source of noise. We focus here on Spectroscopic Ellipsometry (SE) results (in the 0.75 ÷ 5 eV spectral range) obtained on high quality Ta₂O₅ films deposited on SiO₂ substrates by Double Ion Beam Sputtering at the Laboratoire des Matériaux Avancés (Lyon, France). The films are extremely flat as indicated by the 0.2 nm RMS roughness determined by Atomic Force Microscopy (AFM) on (20 × 20) μm² areas. The comparison of the optical properties determined by SE with literature data, corroborated by X-ray Photoelectron Spectroscopy (XPS) data, suggests that the films present a non-ideal bulk stoichiometry and/or some degree of nanoporosity. The possible influence of an interface layer is also discussed.     

Influence of annealing treatments for ZnO-doped Zr0.8Sn0.2TiO4 thin films by RF magnetron sputtering

Zirconium tin titanium oxide doped 1 wt.% ZnO thin films on n-type Si substrate were deposited by rf magnetron sputtering at a fixed rf power of 300 W, a substrate temperature of 450 °C, a deposition pressure of 5 mTorr and an Ar/O₂ ratio of 100/0 with various annealing temperatures and annealing times. Electrical properties and microstructures of 1 wt.% ZnO-doped (Zr_0.8Sn_0.2)TiO₄ thin films prepared by rf magnetron sputtering on n-type Si(100) substrates at different annealing temperatures (500 °C-700 °C) and annealing times (2 h-6 h) have been investigated. The structural and morphological characteristics analyzed by X-ray diffraction (XRD) and atomic force microscope (AFM) were sensitive to the treatment conditions such as annealing temperature and annealing time. At an annealing temperature of 600 °C and an annealing time of 6 h, the ZnO-doped (Zr_0.8Sn_0.2)TiO₄ thin films possess a dielectric constant of 46 (at f = 10 MHz), a dissipation factor of 0.059 (at f = 10 MHz), and a low leakage current density of 3.8 × 10^− 9 A/cm² at an electrical field of 1 kV/cm.     

Photocatalytical water decomposition on visible light-driven solid-solution compounds K4Ce2Ta10−xNbxO30 (x = 0-10)

A series of single phase solid-solution K₄Ce₂Ta_10−xNb_xO₃₀ (x = 0-10) photocatalysts were synthesized by conventional high temperature solid state reaction. Their UV-vis diffuse reflectance spectra showed their absorbance edges shifted to long wavelength zone consistently with the increase of the amount of Nb for substituting Ta in these compounds, and the onsets of absorbance edges ranging from about 540 nm to 690 nm, corresponding to bandgap energy of 1.8-2.3 eV. These series of photocatalysts possess appropriate band gap (ca. 1.8-2.3 eV) and chemical level to use solar energy to decompose water into H₂, and the photocatalytical activities under visible light (λ > 420 nm) demonstrated that the activities decreased correspondingly with the increase of the amount of Nb in these compounds, which is regarded as the result of the differences of their band structures. Furthermore, the photocatalytical activities and the photophysical properties of these visible light-driven photocatalysts K₄Ce₂Ta_10−xNb_xO₃₀ (x = 0-10) were bridged by the first principle calculation based on Density Functional Theory with General Gradient Approximation and Plane-wave Pseudopotential methods.     

Ta3N5 photoanodes for water splitting prepared by sputtering

Ta₃N₅ thin-film photoelectrodes were prepared using a reactive sputtering technique, and their properties for photoelectrochemical water splitting under visible light were investigated. The crystal phases of the films were dependent on the sputtering conditions, such as the N₂/O₂ ratio of the sputtering atmosphere and the substrate temperature (T_s). Single-phase Ta₃N₅ films were obtained by sputtering at N₂/O₂ = 30 and T_s = 1013 K with post-annealing in an NH₃ flow. The Ta₃N₅ photoelectrodes had an anodic photoresponse in water photoelectrolysis, although the photocurrent rapidly decreased because of self-oxidation of the photoanode by photogenerated holes. However, modification of the NH₃-treated Ta₃N₅ films with IrO₂ promoted the oxidation of water and suppressed the self-oxidation of Ta₃N₅.     

Optical and dielectric properties of CuAl2O4 films synthesized by solid-phase epitaxy

The synthesis and properties of CuAl₂O₄ thin films have been examined. The CuAl₂O₄ films were deposited via reactive direct current magnetron sputter using a CuAl₂ target. As-deposited films were amorphous. Post-deposition annealing at high temperature in oxygen yielded solid-phase epitaxy on MgO. The film orientation was cube-on-cube epitaxy on (001) MgO single-crystal substrates. The films were transparent to visible light. The band gap of crystalline CuAl₂O₄ was determined to be ∼ 4 eV using a Tauc plot from the optical transmission spectrum. The dielectric constant of the amorphous films was determined to be ∼ 20-23 at 1-100 kHz.     

Magnetron sputtering of TiOxNy films

This article reports on the characterization and preparation of N-doped titanium dioxide (TiO₂) films by reactive magnetron sputtering from Ti(99.5) targets in a mixture of Ar/O₂/N₂ atmosphere on unheated glass substrates. A dual magnetron system supplied by a dc bipolar pulsed power source was used to sputter the TiO_xN_y films. The amount of N in the TiO_xN_y film ranges from 5 to 40 at%. Its structure was measured using X-ray diffraction (XRD), the optical band gap was calculated from Tauc plots and the decrease of the water contact angle α_ir after the film activation by UV irradiation was investigated as a function of at% of N in the TiO_xN_y film. The yellow-coloured TiO_xN_y films with high (≈8 at%) amount of N exhibited a strong decrease of the band gap E_g down to 2.7 eV. A significant decrease of the water contact angle α_ir after UV irradiation has been observed for 2 μm thick transparent nanocrystalline (anatase+rutile) N-doped TiO₂ films containing less than 6 at% of N.     

Preparation of ZrNxOy films by magnetron sputtering using air as a reactive gas

Zirconium oxynitride (ZrN_xO_y) thin films were prepared by d.c. magnetron sputtering using air as a reactive gas. Replacing conventionally used N₂/O₂ with air as a reactive gas allows the process to perform at high base pressures (low vacuum), which could drastically reduce the processing time. The color of the obtained films changed from light golden and dark golden for low air/Ar flow ratios, to dark violet and bright cyan for high air/Ar ratios. X-ray diffraction patterns show that the films transformed from ZrN and Zr₂ON₂ mixed phases to a Zr₂ON₂ phase, and then an m-ZrO₂ phase. The thickness of the films decreased slightly with increasing the air/Ar flow ratio. ZrN_xO_y films possessed a mixture of Zr-N-O, Zr-N and Zr-O chemical binding states determined from X-ray photoelectron spectroscopy. ZrN_xO_y films with mainly a Zr₂ON₂ phase exhibited the band gap of 1.96-2.26 eV, while the m-ZrO₂ films with slight nitrogen incorporation had a band gap of 2.32 eV, evaluated from transmittance spectra. By varying the air/Ar ratio during deposition, the nitrogen/oxygen content of the films could be controlled and hence, the color, crystal structure, atomic composition, and band gap of the films could be tailored.     

Fabrication of Ta3N5-Ag nanocomposite thin films with high resistivity and near-zero temperature coefficient of resistance

In this study, we investigate as-deposited Ta₃N₅-Ag nanocomposite thin films with near-zero temperature coefficients of resistance (TCRs) that are fabricated by a reactive co-sputtering method; these films can be used in thin-film embedded resistors. In these films, the TCR approaches zero due to compensation between Ag (+TCR) and Ta-N (−TCR) at resistivities higher than 0.005 Ω-cm.Taking into account the fact that Ag counterbalances the resistivity of the Ta₃N₅-Ag thin film, we performed reactive co-sputtering at a nitrogen partial pressure of 55%, corresponding to a resistivity of 0.384 Ω-cm. The resistivity and power density changed, respectively, from 1.333 Ω-cm and 0.44 W/cm² for silver to 0.0059 Ω-cm and 0.94 W/cm² for the Ta₃N₅-Ag thin film. A near-zero TCR of + 34 ppm/K was obtained at 0.94 W/cm² in the Ta₃N₅-Ag thin film without heat treatment.     

Effect of the composition on the bandgap width of high-κ MexTiyOz (Me = Hf, Ta, Sr) layers

To explore the possibility of bandgap engineering in Ti-oxide based insulators, we investigated the effect of added cations of another kind (Hf, Ta, Sr) on the optical absorption and photoconductivity of thin titanate films. A bandgap of 3.1-3.4 eV, typical for pure polycrystalline TiO₂, was found in crystallized Sr_xTi_yO_z of different composition as well as in amorphous Ta₂Ti₃O_z. By contrast, the gap width of Hf titanates increases starting from 3.5 eV for 30% Hf/(Hf + Ti) to 4.2 eV for 84% Hf/(Hf + Ti). We suggest that this gap widening is associated with reduced interaction between electron states of neighboring Ti cations as influenced by a wide-gap (E_g = 5.6 eV) HfO₂ sub-network.     

Nanocluster evolution in Ge ion implanted Ta2O5 layers

Ion implantation-induced nanoclusters were synthesized in reactive sputtered Ta₂O₅ films by Ge⁺ implantation and subsequent annealing. The effects of ion fluence and post-implantation thermal treatment on the kinetics of the nanoclustering were investigated. Ge⁺ ions with energy of 40 keV and fluences of 5 × 10¹⁵, 1 × 10¹⁶ and 5 × 10¹⁶ cm^− 2 were implanted in the Ta₂O₅ layers at room temperature. The samples were thermally treated by rapid thermal annealing in vacuum at 700 °C and 1000 °C for 30, 60 and 180 s. Structural studies of all samples were done by Cross-sectional Transmission Electron Microscopy in diffraction and phase contrast mode. Under optimized conditions (high implantation fluence, subsequent annealing) nanoclusters are formed around the projected ion range of the implanted Ge⁺ ions. The structure of the implanted Ta₂O₅ matrix changes from amorphous to orthorhombic when the annealing was performed at 1000 °C. Although the Ta₂O₅ matrix crystallizes, no evidence is obtained for crystallization of the embedded nanoclusters even after annealing at 1000 °C.     

Cadmium oxide, indium oxide and cadmium indate thin films obtained by the sol-gel technique

Thin films of the mixed CdO-In₂O₃ system were deposited on glass substrates by the sol-gel technique. The precursor solution was obtained starting from the mixture of two precursor solutions of CdO and In₂O₃ prepared separately at room temperature. The In atomic concentration percentages (X) in the precursor solution with respect to Cd (1 − X), were: 0, 16, 33, 50, 67, 84 and 100. The films were sintered at two different sintering temperatures (Ts) 450 and 550 °C, and after that, annealed in a 96:4 N₂/H₂ gas mixture at 350 °C. X-ray diffraction patterns showed three types of films, excluding those constituted only of CdO and In₂O₃ crystals: i) For X ≤ 50 at.%, the films were constituted of CdO + CdIn₂O₄ crystals, ii) For X = 67 at.%, the films were only formed of CdIn₂O₄ crystals and iii) For X = 84 at.% the films were constituted of In₂O₃ + CdIn₂O₄ crystals. In all films in the 0 < X < 100 range, the formation CdIn₂O₄ crystals of this material was prioritized with respect to the formation of CdO and In₂O₃ materials. All films showed high optical transmission and an increase of the direct band gap value from 2.4 (for CdO) to 3.6 eV (for In₂O₃), as the X value increases. The resistivity values obtained were in the interval of 8 × 10^− 4 Ω cm to 10⁶ Ω cm. The CdIn₂O₄ films had a resistivity value of 8 × 10^− 3 Ω cm and a band gap value of 3.3 eV.     

Conducting and topographic AFM analysis of Hf-doped and Al-doped Ta2O5 films

A conductive atomic force microscopy (C-AFM) has been used to study conductivity and electrical degradation of ultrathin (4 nm) Hf- and Al-doped Ta₂O₅ at the nanometer scale. The hardness testing has been also performed using the force measuring ability of the AFM. Since the size of the analyzed area is very small, features which are not visible by macroscopic tests are observed: extremely low leakage current (~ pA) up to significantly higher than the fields during standard current-voltage measurements; charge trapping/detrapping processes manifesting as current peaks at pre-breakdown voltages. Hf and Al addition improves the local conductivity of Ta₂O₅, provokes modification of the leakage current mechanism, and is effective in extending the potential of pure Ta₂O₅ as a high-k material at the nanoscale. The results point to a decisive role of the type of the dopant on the electrical and mechanical properties of the films and their local response to short term microwave irradiation. Hf-doped Ta₂O₅ exhibits excellent electrical stability and high hardness. Al doping provides more plastic films with large electrical inhomogeneities; the microwave treatment at room temperature is a way to improve these parameters to a level comparable to those of Hf-doped films.     

Synthesis of K6Ta10.8O30 nanowires by molten salt technique

The synthesis of single crystalline K₆Ta_10.8O₃₀ nanowires by molten salt method was reported for the first time. X-ray diffraction results indicated that the as-prepared products were pure phase K₆Ta_10.8O₃₀. Scanning electron microscopy and transmission electron microscopy results showed that the products consisted of wire-like nanostructures with 100-300 nm in diameter and several micrometers in length. High resolution electron microscopy and selected area electron diffraction results indicated that the K₆Ta_10.8O₃₀ nanowires were single crystalline with a growth direction of [0 0 1]. The ultraviolet-visible diffuse reflectance measurement showed that the band gap of the nanowires was about 4.1 eV. The effects of reaction temperature, time, and weight ratio of the precursor (mixture of K₂CO₃ and Ta₂O₅) to KCl salt on the morphology of the products were investigated.