Photo-fixation of SO2 in nanocrystalline TiO2 films prepared by reactive DC magnetron sputtering

We report on photo-fixation of SO₂ onto nanostructured TiO₂ thin films prepared by reactive DC magnetron sputtering. The films were exposed to 50 ppm SO₂ gas mixed in synthetic air and illuminated with UV light at 298 and 473 K. The evolution of the adsorbed SO_x species was monitored by in situ Fourier transform infrared specular reflection spectroscopy. Significant photo-fixation occurred only in the presence of UV illumination. The SO₂ uptake was dramatically enhanced at elevated temperatures and then produced strongly bonded surface-coordinated SO_x complexes. The total SO_x uptake is consistent with Langmuir adsorption kinetics. The sulfur doping at saturation was estimated from X-ray photoelectron spectroscopy to be ~ 2.2 at.% at 473 K. These films were pale yellowish and had an optical absorption coefficient being ~ 3 times higher than in undoped film. The S-doped films exhibit interesting oleophobic properties, exemplified by the poor adherence of stearic acid. Our results suggest a new method for sulfur doping of TiO₂ to achieve combined anti-grease and photocatalytic properties.     

Thermal stability of sputtered zirconium oxide films

In this work, the effect of post-growth annealing on the structural and optical properties of sputtered zirconium oxide films has been investigated. The temperature dependence of structure, density, and optical constants has been systematically studied by X-ray diffraction, X-ray reflectometry, atomic force microscopy (AFM) and optical spectroscopy. X-ray diffraction studies show no variation in the crystalline phase upon annealing except grain growth. X-ray reflectivity measurements determine a density increase of approximately 11% and a simultaneous thickness reduction of 10% upon annealing. The surface roughness of the films increases upon annealing as determined by XRR and confirmed by AFM measurements. Optical spectroscopy measurements confirm that the refractive index n of the films decreases with increasing annealing temperature. At the same time the optical band gap E_g of the films increases from 4.58 to 4.97 eV annealing at 900°C. The surprising decrease of refractive index upon annealing is attributed to both the intermixing of Si with ZrO₂ and the increasing surface roughness of the films.     

Varistor performance of nanocrystalline Zn-Bi-O thin films prepared by reactive RF magnetron sputtering at room temperature

The Zn-Bi-O films were deposited by reactive radio frequency magnetron sputtering in oxygen atmosphere from ZnBi alloy target (wt% ratio Zn:Bi=9:1) on glass substrate at room temperature. The XRD patterns show that the films deposited on tin-doped indium oxide/glass substrates were nanocrystalline. The microstructure of Bi-doped ZnO films was studied by scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. All the obtained layers had varistor-type non-linear current-voltage (I-V) characteristics with low breakdown voltage varying from few tenths of a volt to few volts.     

Substrate and annealing temperature effects on the crystallographic and optical properties of MoO3 thin films prepared by laser assisted evaporation

MoO₃ thin Films were prepared using the assisted laser evaporation technique. Samples were grown on glass and silicon substrates at different substrates temperatures. The effect on structural and optical properties of the substrate and on annealing temperatures was evaluated. A phase transition was found around 200 °C in all samples from the amorphous to the β phase with a small percentage of α phase, and another one was found around 500 °C from the α + β to the α phase. The percentage errors between the lattice parameter a₀ of the crystallographic index card for the MoO₃ alpha phase and the indexed lattice parameters were 1.4% and 0.3% for the samples deposited on glass and silicon respectively, indicating the crystalline structure of the silicon substrate favors the formation of the MoO₃ alpha orthorhombic phase. The spectral variation of the refractive index and the absorption coefficient were theoretically determined. The amorphous samples presented a constant gap of 3.2 eV while the optical properties critically depended on the substrate and annealing temperatures.     

Fabrication of YbAl3 film via annealing amorphous Yb-Al film deposited by RF magnetron sputtering

YbAl₃ single-phase bulk alloy was synthesized by melting at 1258 K using raw Yb and Al metals in the ratio of 1:2.2. A sputtering YbAl₃ target was prepared using the precursor YbAl₃ bulk alloy with the spark plasma sintering process. An amorphous Yb-Al film was fabricated by RF magnetron sputtering using the YbAl₃ target, and a single-phase crystalline YbAl₃ film was fabricated by annealing the amorphous Yb-Al film at temperatures higher than 923 K in Ar atmosphere.     

Optical properties of nanocrystalline ZnS films prepared by high pressure magnetron sputtering

Nanocrystalline ZnS films with different thickness (10–40 nm) were deposited onto quartz and NaCl substrates by magnetron sputtering of a ZnS target in argon plasma. All the films showed a zinc blende structure and the photoluminescence peak positions depended on the surface to volume ratio of the films. The optical absorption in these films could be explained by the combined effects of phonon and inhomogeneity broadening along with optical loss due to light scattering at the nanocrystallites.     

Structural analysis of amorphous Si films prepared by magnetron sputtering

A study is presented on the structural changes occurring in thin amorphous silicon (a-Si) during thermal treatments. The a-Si films were deposited on single-crystalline Si substrates held at room temperature by magnetron sputtering of a Si target in pure Ar atmosphere, and therefore the films were hydrogen-free. All samples were annealed in vacuum and subsequently studied by electron paramagnetic resonance (EPR) and grazing incidence X-ray diffraction (GIXRD). A slight increase in the dangling bonds content at lower annealing temperatures, and then a strong increase of it at around 650 °C, suggested significant structural changes. The samples were also studied by grazing incidence small-angle X-ray scattering (GISAXS) which confirmed changes at the nanometric scale attributed to voids in the material. A nice correlation of the results of the three techniques shows advantages of this approach in the analysis of structural changes in a-Si material.     

Structural and optical properties of yttrium trioxide thin films prepared by RF magnetron sputtering

Yttrium trioxide (Y₂O₃) thin films have been deposited on silicon (111) at different RF powers and the sputtering pressures by RF magnetron sputtering. The influences of the RF power and the sputtering pressures on the structural and optical properties of Y₂O₃ thin films were investigated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscope (AFM) and spectroscopic ellipsometer (SE). The results show that chemical composition of as-deposited Y₂O₃ film is apparently close to the stoichiometric ratio and it is crystallized but crystallinity is poor. The monoclinic and cubic fluorite-like structure can coexist in as-deposited Y₂O₃ film. A four-layer-structured optical model consisting of silicon substrate, silicon dioxide (SiO₂) interlayer, Y₂O₃ layer and a surface roughness (SR) layer is built for interpreting preferably the results measured by spectroscopic ellipsometry. With the increase of RF power or decrease of sputtering pressure, the refractive index and optical bandgap of sputtered Y₂O₃ film is increased and the extinction coefficients is decreased.     

Photocatalytic Zn-doped TiO2 films prepared by DC reactive magnetron sputtering

Zn-doped TiO₂ films were prepared by means of pulsed DC reactive magnetron sputtering method using Ti and Zn mixed target. The deposition condition was optimized to produce uniform and transparent TiO₂ films. Titanium was in the Ti⁴⁺ oxidation state in all Zn-doped TiO₂ films. The zinc oxide deposited on the substrate was in the fully oxidized state of ZnO. Increase of zinc concentration inhibited the crystal growth in the TiO₂ films. The surface morphology gradually changed from crystalline to amorphous along with the increase of doped zinc concentration. The optical transmittances of these films decreased only slightly with increasing zinc concentration due to very similar band edges of ZnO and anatase TiO₂. The doped ZnO had weak influence on light absorption of the TiO₂ films. When zinc concentration was very low (<1 at%), the photocatalytic activities of the doped films had nearly no difference from that of pure TiO₂ film. Photocatalytic activities decreased obviously in the films containing high amount of zinc oxide.     

Optical and structural properties of vanadium pentoxide films prepared by d.c. reactive magnetron sputtering

Vanadium pentoxide films were deposited onto glass substrates at different substrate temperatures (RT—400 °C) by d.c. reactive magnetron sputtering. The structural properties of the films were studied by X-ray diffraction, scanning electron microscopy and Raman spectra. The optical properties of the films were studied by measuring and fitting the transmittance. The film prepared at low temperature showed a high optical transmittance. The film prepared at the substrate temperature lower than 200 °C has an amorphous structure and the film prepared at substrate temperatures higher than 200 °C had a polycrystalline V₂O₅ structure. The optical parameters of the films were calculated by fitting the transmittance using the classical model.     

Indium tin oxide films deposited on polyethylene naphthalate substrates by radio frequency magnetron sputtering

Indium tin oxide (ITO) thin films were deposited on unheated polyethylene naphthalate substrates by radio-frequency (rf) magnetron sputtering from an In₂O₃ (90 wt.%) containing SnO₂ (10 wt.%) target. We report the structural, electrical and optical properties of the ITO films as a function of rf power and deposition time. Low rf power values, in the range of 100-130 W, were employed in the deposition process to avoid damage to the plastic substrates by heating caused by the plasma. The films were analyzed by X-ray diffraction and optical transmission measurements. A Hall measurement system was used to measure the carrier concentration and electrical resistivity of the films by the Van der Pauw method. The X-ray diffraction measurements analysis showed that the ITO films are polycrystalline with the bixbite cubic crystalline phase. It is observed a change in the preferential crystalline orientation of the films from the (222) to the (400) crystalline orientation with increasing rf power or deposition time in the sputtering process. The optical transmission of the films was around 80% with electrical resistivity and sheet resistance down to 4.9 × 10^- 4 Ωcm and 14 Ω/sq, respectively.     

反应射频磁控溅射法制备HfTaO薄膜的热稳定性和光学性能

采用反应射频磁控溅射技术制备HfTaO薄膜,利用X射线衍射(XRD)分析了薄膜的微结构,通过紫外-可见光分光光度计测量了薄膜的透过谱,计算了薄膜的折射率和禁带宽度,利用原子力显微镜观察了薄膜的表面形貌。结果表明,随着Ta掺入量(10%,26%,50%)的增加,HfTaO薄膜的结晶化温度分别为800、900、950℃,Ta掺入量继续增加到72%,经过950℃退火处理的HfTaO薄膜仍然保持非晶态,具有优良的热稳定性。AFM形貌分析显示非晶HfTaO薄膜表面非常平整。在550nm处薄膜折射率n随着Ta掺入量的增大而增大,n的变化区间为1.90～2.15。同时HfTaO薄膜的光学带隙Eg随着Ta掺入量的增大而逐渐减小,Eg的变化区间为4.15～5.29eV。     

Electrical and optical properties of nanostructured VOX thin films prepared by direct current magnetron reactive sputtering and post-annealing in oxygen

Nanostructured vanadium oxide (nano-VO_X) thin films were prepared by direct current magnetron reactive sputtering in mixed O₂/Ar discharges and subsequent annealing in oxygen atmosphere. X-ray diffraction and field emission scanning electron microscope were employed to characterize the crystal structures and morphologies, respectively. Fourier transform infrared spectroscopy was applied to analyze the vanadium-oxygen bonds of films. X-ray photoelectron spectroscopy revealed the compositions of the surface and inner portion of nano-VO_X thin films. It was shown that the as-deposited films were amorphous, and in-situ annealing of these films in ambient oxygen for 10 min can lead to the growth of nano-VO_X thin films. Results of electrical studies indicated that the absolute values of temperature coefficient of resistance and activation energy of films increased significantly after oxygen annealing. Optical investigations carried out in the UV-visible range showed that the absorption edges of nano-VO_X films exhibited large red shifts compared with as-deposited film, and that dual optical absorptions were observed in nano-VO_X films.     

Properties of ZrNx films with x > 1 deposited by reactive radiofrequency magnetron sputtering

Thin ZrN_x films have been prepared by reactive radiofrequency magnetron sputtering varying the nitrogen partial pressure in the range 0-3.26 Pa. The films have been analyzed by X-ray photoelectron spectroscopy (XPS) and by optical characterization in the UV-Vis-IR range. The cross-section and surface morphology of the samples were examined by means of field emission gun-scanning electron microscopy. The effects of the nitrogen partial pressure on the ZrN_x films stoichiometry have been studied correlating the N 1s photoelectron peaks with different bounding states for the zirconium nitride. The XPS depth profile analysis has revealed the presence of metastable phases (ZrN₂, Zr₃N₄) that vanishes when lowering the nitrogen partial pressure. The optical analysis has permitted to distinguish two different behaviours of the deposited samples in the visible range: semi-transparent and absorbent. Drude-Lorentz model fitted the behaviour of absorbent films, while the O'Leary model was applied to the semi-transparent ones. The semi-transparent films had a band gap varying between 2.36 and 2.42 eV, typical values of N-rich zirconium nitride films. Morphological analysis showed a compact and dense columnar structure for all the samples. A simple growth model explains the presence of the different nitride phases considering implantation and re-sputtering effects.     

Preliminary studies on molybdenum-doped indium oxide thin films deposited by radio-frequency magnetron sputtering at room temperature

Thin films of molybdenum-doped indium oxide (IMO) were prepared by a 3-source, cylindrical radio-frequency magnetron sputtering at room temperature. The films were post-annealed and were characterized by their structural (X-ray diffraction) and optical (UV-VIS-NIR spectrophotometer) properties. The films were studied as a function of oxygen volume percentage (O₂ vol.%) ranging from 3.5 to 17.5. The structural studies revealed that the as-deposited amorphous films become crystalline on annealing. In most cases, the (222) reflection emerged as high intensive peak. The poor visible transmittance of the films as-deposited without oxygen was increased from ∼ 12% to over 80% on introducing oxygen (3.5 O₂ vol.%). For the films annealed in open air, the average visible transmittance in the wavelength ranging 400-800 nm was varied between 77 and 84%. The films annealed at high temperatures (> 300 °C) decreased the transmittance to as low as < 1%. The optical band gap of the as-deposited films increased from the range 3.83-3.90 to 3.85-3.98 eV on annealing at different conditions.     

Property variations of direct-current reactive magnetron sputtered copper oxide thin films deposited at different oxygen partial pressures

Cuprous oxide (Cu₂O) and cupric oxide (CuO) thin films were deposited on glass substrates at different oxygen partial pressures by direct-current reactive magnetron sputtering of pure copper target in a mixture of argon and oxygen gases. Oxygen partial pressure was found to be a crucial parameter in controlling the phases and, thus, the physical properties of the deposited copper oxide thin films. Single-phase Cu₂O thin films with cubic structure were obtained at low oxygen partial pressure between 0.147 Pa and 0.200 Pa while higher oxygen partial pressure promoted the formation of CuO thin films with base-centered monoclinic structure. Polycrystalline Cu₂O thin films deposited with oxygen partial pressure at 0.147 Pa possessed the lowest p-type resistivity of 1.76 Ω cm as well as an optical band gap of 2.01 eV. On the other hand, polycrystalline CuO thin films deposited with oxygen partial pressure at 0.320 Pa were also single phase but showed a n-type resistivity of 0.19 Ω cm along with an optical band gap of 1.58 eV.     

High-permittivity and low-loss dielectric tunable pyrochlore thin films deposited by radio frequency magnetron sputtering from a lead zinc niobate target

Since Bi₂O₃-ZnO-Nb₂O₅ (BZN) pyrochlore thin films have been introduced as a tunable dielectric, the substitution of Bi with Pb could be a reasonable choice. The PbO-ZnO-Nb₂O₅ (PZN) cubic pyrochlore thin films were produced by radio frequency sputtering, and their dielectric properties, in terms of tunability, were measured. Up to 33.4% of tunability and comparable K factors with BZN films were obtained. The effects of film crystallization, along with substrate heating and post-annealing on the dielectric properties, were similar to those of BZN. However, strong texturing developed in the PbO-ZnO-Nb₂O₅ (PZN) films deposited at a high substrate temperature, which caused degradation of the loss tangent and K factor.     

氧分压对TiO2膜结构与光学性质的影响

报道了用反应溅射法制备TiO2 膜的实验研究 .详细研究了膜的沉积、膜结构及其光学性质 ,随溅射氧分压的变化 .随氧分压由 6× 10 - 2 Pa增加到 9× 10 - 2 Pa时 ,晶体结构由金红石变到锐钛矿 ,氧分压超过 9× 10 - 2 Pa时趋向于无定形结构 .与膜结构密切相关的折射率n随氧分压的增大由 2 .4 4变到 1.96 ,禁带宽度Eg 则由大变小 ,然后再增大的变化 (3.4 1→ 3.2 6→3.4 2 ) .     

Study of FePt films prepared by reactive sputtering

In the present study, ⁵⁷FePt films are prepared with reactive ion beam sputtering using mixture of argon and nitrogen gases. Energy-dispersive X-ray reflectivity is used to estimate the thickness of the as-deposited films. Structural and magnetic properties of the as-deposited and annealed films are studied using grazing incidence X-ray diffraction (GIXRD), magneto-optical Kerr effect (MOKE) and conversion electron Mossbauer spectroscopy (CEMS). Significant difference in structural and magnetic properties i.e., formation of ordered L1₀ phase and perpendicular magnetic anisotropy are observed for the films prepared with mixture of nitrogen and argon as compared to the film prepared with argon only. From the GIXRD, peaks corresponding to the ordered face-centred tetragonal FePt phase are observed for the films prepared with mixture gas. The results of CEMS clearly show the perpendicular magnetic anisotropy (PMA) for the films prepared with mixture of nitrogen and argon. The observed enhanced chemical ordering and the development of PMA in the films prepared with mixture gas is due to the role played by the defects created as a consequence of nitrogen escape in the films with high temperature annealing.     

Effect of base and oxygen partial pressures on the electrical and optical properties of indium molybdenum oxide thin films

Indium molybdenum oxide thin films were RF sputtered at room temperature on glass substrates with a reference base pressure of 7.5 × 10^− 4 Pa. The electrical and optical properties of the films were studied as a function of oxygen partial pressures (OPP) ranging from 1.5 × 10^− 3 Pa to 3.5 × 10^− 3 Pa. The obtained data show that the bulk resistivity of the films increased by about 4 orders of magnitude (from 7.9 × 10^− 3 to 7.6 × 10¹ Ω-cm) when the OPP increased from 1.5 × 10⁻³ to 3.5 × 10^− 3 Pa, and the carrier concentration decreased by about 4 orders (from 1.77 × 10²⁰ to 2.31 × 10¹⁶ cm^− 3). On the other hand, the average visible transmittance of 30.54% of the films (brown colour; OPP = 1.5 × 10^− 3 Pa) was increased with increasing OPP to a maximum of 80.47% (OPP = 3.5 × 10^− 3 Pa). The optical band gap calculated from the absorption edge of the transmittance spectra ranges from 3.77 to 3.88 eV. Further, the optical and electrical properties of the films differ from those deposited at similar conditions but with a base pressure lower than 7.5 × 10^− 4 Pa.